School of Chemistry and Biochemistry Georgia Institute of Technology Atlanta GA 30332-0400 USA
Department of Chemistry The University of Akron Akron OH 44325-3601 USA
School of Chemistry and Biochemistry Georgia Institute of Technology Atlanta GA 30332-0400 USA, Nuclear and Radiological Engineering Program Georgia Institute of Technology Atlanta GA 30332-0400 USA
The study of the redox chemistry of mid‐actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non‐aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] − ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1‐M , 2‐M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well‐behaved Np 5+/4+ redox couple. The differences in the chemical redox properties of the U vs . Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.
Otte, Kaitlyn S., Niklas, Julie E., Studvick, Chad M., Boggiano, Andrew C., Bacsa, John, Popov, Ivan A., & La Pierre, Henry S. (2023). Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**. Angewandte Chemie, 135(34). https://doi.org/10.1002/ange.202306580
Otte, Kaitlyn S., Niklas, Julie E., Studvick, Chad M., et al., "Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**," Angewandte Chemie 135, no. 34 (2023), https://doi.org/10.1002/ange.202306580
@article{osti_1994887,
author = {Otte, Kaitlyn S. and Niklas, Julie E. and Studvick, Chad M. and Boggiano, Andrew C. and Bacsa, John and Popov, Ivan A. and La Pierre, Henry S.},
title = {Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**},
annote = {Abstract The study of the redox chemistry of mid‐actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non‐aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] − ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1‐M , 2‐M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well‐behaved Np 5+/4+ redox couple. The differences in the chemical redox properties of the U vs . Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory. },
doi = {10.1002/ange.202306580},
url = {https://www.osti.gov/biblio/1994887},
journal = {Angewandte Chemie},
issn = {ISSN 0044-8249},
number = {34},
volume = {135},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2023},
month = {07}}